This invention relates to certain new materials capable of imparting anti-wear properties to industrial fluids such as hydraulic fluids and gear oils.

It is known that zinc-based additives can be included in industrial fluids such as gear oils to impart high performance wear resistance. However, it is desired to move away from the use of materials containing zinc which cause problems in use, such as hydrolytic stability, to additives which are zinc free and ashless. While certain phosphorus containing additives, such as tri-alkyl or tri-aryl phosphates, have been proposed for other purposes in industrial fluids, there has been nothing, in any way, to suggest their use as anti-wear additives which would be capable of matching or improving upon the performance of the presently employed zinc-based additives.

Accordingly, the present invention provides a zinc-free anti-wear additive composition for an industrial fluid comprising as an active anti-wear ingredient an amine phosphate which is the reaction product of at least one n-heptyl acid phosphate with at least one aliphatic amine having at least 9 carbon atoms, preferably at least 12 carbon atoms.

The n-heptyl acid phosphate may be the monoheptyl phosphate or diheptylphosphate or a mixture thereof, suitably a mixture of about 50% mono and 50% diheptyl phosphate.

The aliphatic amine preferably has at least 12 carbon atoms. The aliphatic moiety is preferably an alkyl, alkenyl or alkoxyalkyl group. The amine is preferably a p_-amine. Suitable amines are the C ₁₂ . ₁₄ alkylamine available commercially as "Primene 81 R" from the Rohm and Haas Company

or the C ₁₈ alkenylamine of formula H ₂ N(CH ₂ ) ₇ = (CH,),, available commercially as "Armeen O" from Akzo Chemie Nederland BV, or "Radiamine 6172" from Petrofina s.a., Belgium. Alternatively, an alkoxyalkylamine such as 3-isononyloxypropylamine (available from Hoechst AG) may be employed.

The amine phosphate active ingredients based on C ₇ acid phosphates are new per se and are, therefore, included within the scope of the invention.

The additive composition of the invention can be employed in a variety of base fluids including conventional mineral based fluids, such as BP Virgin, or may also be used in natural or synthetic ester based fluids.

The concentration of the amine phosphate ingredient will be selected dependent on the base fluid chosen and the intended use of the fluid. It has been found that, for hydraulic use, using a mineral base fluid, a preferred concentration is at least about 0.05 and preferably at least 0.09 percent by weight, while for gear oil use, the preferred concentration of amine phosphate is at least about 0.09 and preferably at least 0.17 percent by weight. The upper limit of a satisfactory concentration range can be established dependent on economic considerations and required performance.

The additive composition may contain a wide variety of additives in addition to the amine phosphate. Thus, dependent on the end use, the composition may contain a polysulphide load carrying and anti-wear material. Other additives which may be used include dialkylhydrogen phosphite or tri-alkyl or tri-aryl phosphates (for the purpose of load carrying and anti-wear), copper passivators, such as alkyl dithiadiazoles and benzotriazole derivatives, alkyl p-amines (for the purpose of corrosion inhibition and anti-wear), antifoam

agents such as silicon based or non-silicon Mobilad C402 and anti-oxidants such as 2,6-di-tert-butyl-4-methyl phenol, Additin 10 from Rhein Chemie Rheinau GmbH and Irganox 57 from Ciba-Geigy Industrial Chemicals. The exact composition will depend on the intended use and nature of the base fluid.

The amine phosphate may be prepared by directly reacting the amine with the N-heptyl acid phosphate (preferably in substantially equimolar proportions), followed by cooling of the reaction mixture which is exothermic. The product is then incorporated with the other additive components to produce an additive composition for incorporation at appropriate concentration in the base fluid.

Alternatively, the amine phosphate may be prepared in situ by separately adding to a suitable diluent the acid phosphate and the amine and blending, suitably at elevated temperature, for example, about 60 ^S C before adding the remaining additives, thus avoiding any problems of exothermicity. The diluent may be the, or one or more of the, major components of the composition, suitably a polysulphide component but it will be appreciated that the diluent may be, for example, the ultimately intended base fluid, such as BP base fluid. Preferably the composition includes a dialkyl hydrogen phosphite which is suitably added after the other additives such as copper passivators, corrosion inhibitors, anit-foam agents and antioxidants.

The invention will now be illustrated with reference to the following examples.

Example 1 Preparation of C ₁₂ . ₁₄ -amine n-heptyl phosphate Projected Formula: /

R = C Hi ₄ C = Cι ₂ - C ₁₄ range

Primene 81 R (a C ₁₂ . _u amine available from Rohm and Haas) was added to a glass lined (or stainless steel) vessel. rvHeptyl acid phosphate (available from Albright and Wilson) or Elf Atochem was added slowly with stirring. The two reactants were employed in the ratio of 59.7% n-heptyl acid phospate to 40.3% Primene 81 R.

The reaction was exothermic. Blending was continued for at least 30 minutes and the reaction mixture allowed to cool.

The resulting product was a light yellow liquid which was characterised by the infrared spectrum (measured by KBr disc) given in Figure 1 and the analytical data below:

Phosphorus 6.80 to 8.49% Nitrogen 2.82 to 3.23% Density (20°C) 0.96 g/ml approx. Flash point (PMC) 92°C min. Viscosity (100°C) 48 mm ² /sec (typical)

Example 2 Preparation of additive composition.

An additive composition suitable for use in a hydraulic fluid or gear oil was prepared by the following alternaitve methods:

A) To a warmed solution of polysulphide (TPS 32 available from Elf Atochem) to which was dissolved the antioxidant (Additin 10), there was added the n-heptyl amine phosphate prepared as described in Example 1 above and other additives as given below followed by blending for a minimum of 30 minutes and cooling.

B) Polysulphide and Additin 10 were added to a blend vessel to which was further added n-heptyl acid phosphate at 6.23% and Primene 81 R at 4.20%. The reaction mixture was heated to a maximum temperature of 60°C and blending continued to. homogeneity and until all the antioxidant (Additin 10) was dissolved. The remaining additives, as given below, were then added, blending continued for a minimum of 30 minutes and the mixture cooled.

The resulting additive composition can be used (depending on the application) as follows in terms of a percentage range (by weight):

Range Example

Polysulphide 50 to 75 61.35

Amine phospate 4 to 28 10.43

Dialkyl hydrogen phosphite 4 to 28 6.14

(e.g. dibutyl hydrogen phosphite)

Copper passivator 6 to 17 3.68

(e.g. thiadiazole passivator)

Alkyl p-amine 4 to 28 7.06

Anti-foam agent 0 to 1 0.30

(e.g. Mobilad C405)

Antioxidants 0 to 12 11.04

(e.g. phenolic/aminic mixture)

The additive composition was obtained in both methods as a yellow amber oily liquid, homogeneous, clear and bright. The infra red spectrum for the product from methods A) and B) is given in Figure 2.

The analytical data is:

Phosphorus 1.50 to 1.94%

Nitrogen 0.99 to 1.30%

Sulphur 17.2 to 23.3%

Density 0.98 g/ml (typical)

Flash Point (PMC) 50°C (min)

Viscosity 100/40°C 10/143c St ^•

Example 3 Use of Additive Composition in Hydraulic Oils

The additive composition described in Example 2 above was blended into base fluids as given in Table 1 below to give two ISO VG 46 to 68 hydraulic oils and subjected to a series of standard tests as given in the Table. It is to be noted that the test results are of the level not normally expected for zinc free ashless compositions. The additive composition has provided a high standard hydraulic oil performance and, in particular, very low wear rates in the Vane pump test.

TABLE 1

^* This formulation contained an additional 0.1% antioxidant

# Additive composition of Example 2 plus additional 0.1% antioxidant.

Example 4 Use of Additive Composition in Gear Oils

The additive composition described in Example 2 above without antioxidants was blended into base fluids as given in Tables 2 and 3 below to give gear oils in the ISO 100 to ISO 320 range. The blends were subjected to a series of standard tests as given in the Tables.

TABLE 2

It will be seen from the above Table that there was provided satisfactory gear oil performance at an additive combination of 1.45% for ISO V.G. 150 and above and an additive treat rate of 1.50% for ISO V.G. 100.

TABLE 3

Example 5 Use of Modified Additive Compositions

Further test fluids were prepared containing additive compositions prepared using the methods described in Examples 1 and 2 and using two alternative amine phosphates (one prepared using ARMEEN O and one prepared using iso-nonyloxypropylamine) and polysulphide and/or dialkyi phosphite additives in an amount of 1.0%/0.09 and 0.1 %. The compositions were tested for anti-wear performance in accordance with IP 239. The compositions and results are given in Table 3 below. The base fluid was B.P. 150 Solvent neutral.

TABLE 4

It can be seen from the above results that the preparation in Example 1 , together with a dialkyi hydrogen phosphite and an amine phospate prepared using ARMEEN O and isononyloxypropylamine produce low anti-wear performance in the IP 239 Shell 4-ball test.

Example 6 Use of Additive Composition in Synthetic Ester Hydraulic Fluids

The additive composition described in Example 2 above was blended into synthetic ester base fluids of the grades given in Table 5 below and subjected to a series of standard tests as given in the Table.

TABLE 5

Grade HE 32 46 68 Limits

ISO Viscosity Grade VG 32 46 68 32/46/68

Pour Point, °C max - 57 -51 - 51 -18/-15/-12

Steel Corrosion, max (DIN Pass Pass Pass Class 0-Method A 51585)

Copper Corrosion 1b 1b 1b Class 2-3 max (DIN 51759) hours at 100°C

Air Release 50 ^C C mins, max (DIN <0.5 <0.5 1.7 5/10/10 51381)

Demulsibiiity, 54 ^C C, mins, max 10 30 45 40/40/60 (DIN 51549)

FZG, A8.3/90: Load Stage >12 >12 >12 10 Fail, min

Vane Pump Wear, mg, max (1)

(DIN 51389/2)

Ring} @ 250 hours (1) 2.5 <120 120

Vanes 7.1 <30 30

Stear stability %, max (DIN - -4.3 - ± 10 51382) 100°C 250 cycles, loss

(1) DIN 51389/2 ® 250 hours

(2) Replaces DIN 51587 used for mineral oil based fluids.

It will be seen from Table 5 that the fluids meet the Baader oxidation test requirement for synthetic ester base fluid hydraulic lubricants with very low viscosity and acid number increase after test. They meet the following lubricant specifications where the oxidation testing used was that developed for ester base fluids.

> DIN 51524, part 2

> SEB 181 - 222 Ford U.MC 006-8004

> Brugger

The lubricants have been found to provide excellent corrosion protection, extreme pressure and anti-wear with a passing result in the Vickers 104C 250 hour vane pump test and very high FZG load stage performance. They are compatible with nitrile, fluorocarbon and polyurethane sealing material and their high viscosity index, low pour point and good filtration ensures that the lubricant properties are excellent.

It has been found that, when used with the applicants' water based metalworking fluids the lubricants show excellent separation properties. Their biodegradability of greater than 95% for the ISO VG 32 and 46 grade and greater than 85% for the ISO VG grade by CEC L33 T82 minimises their impact on the environment as do the properties of being heavy metal, chlorine free and ashless.

Example 7 Use of Additive Composition in Synthetic Ester Gear Oil

The additive composition described in Example 2 above was blended into synthetic ester base fluids of the grades given in Table 6 below and subjected to a series of standard tests as given in the Table.

TABLE 6

TABLE 6 - Continued

(iii) Polyurethane @ 80°C

Volume Change % 0.2 0.6 - - 0 +3/+10

Hardness Change 0 -1 - - -1 -10/+10

Stear stability %, max

(CEC-4-45-T-93/A) 100°C

± 10 loss <10 <10 <10 <10 -8.7

It will be seen from Table 6 that the lubricants meet the following internationally recognised specifications that were originally designed for mineral oil based fluids.

> DIN 51517, part 3

> SEB 181 -222

> Ford U-MC 002-8008

> U.S. Steel 224

> Brugger

We have found that the lubricants provide excellent corrosion protection, extreme pressure and anti-wear performance with an FZG load stage pass greater than 12. They are compatible with nitrile, fluorocarbon and polyurethane sealing material and their high viscosity index, low pour point and good filtration ensures that their lubrication properties are excellent.

Biodegradability of greater than 85% for the 220 grade and greater than 95% for the lower viscosity lubricants minimises the impact on the environment as does the properties of being heavy metal, chlorine free and ashless.